Process for breaking petroleum emulsions



Patented Mar. 7, 1950 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, St. Louis, and Bernhard Keiser, Webster Groves, Mo.,' assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application March 21, 1949, Serial No. 82,704. In Venezuela March 7, 1947 21 Claims.

This invention relates to processes orprocedures particularly adapted for preventing, breaking, or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. This application is in part a continuation of a number of our applications, to wit, Serial No. 518,660 and Serial No. 518,661, both filed January 17, 1944; Serial No. 666,817, Serial No. 666,818 and Serial No. 666,821, all filed May 2, 1946; Serial No. 727,282, filed February '7, 1947; Serial No. 751,608 and Serial No. 751,618, both filed May 31, 1947; Serial No. 8,730, filed February 16, 1948; and Serial No. 42,133,

filed August 2, 1948, all abandoned.

Complementary to the aboveaspect of our invention is our companion invention concerned with the new chemical products or compounds used as the demulsifying agents in said aforementioned processes or procedures, as well as the application of such chemical compounds, products, .and the like, in various other arts and in- "dustries, along with methods for manufacturing said new chemical products or compounds which are of outstanding value in demulsification. See our applications, Serial No. 751,619, filed May 31, 1947 (abandoned) Serial No. 8,731, filed February 16, 1948; and Serial No. 42,134, filed August 2, 1948.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil," roily oil, emulsified oil," etc., and which comprise fine dropletsof naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditionsfrom mineral oil, such as crude oil and relatively soft waters or weak brines, Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

Demulsification as contemplated in the present application includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in the absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.

In our aforementioned copending applications previously referred to, to wit, Serial Numbers 518,660, 518,661, 666,817, 666,821, 727,282 8,730, and 42,133, and in two other copending applications, to wit, Serial Numbers 666,816 and 666,818, both filed May 2, 1946, both now abandoned, we have described certain new products or compositions of matter which are of unusual value in certain industrial applications requiring the use of products or compounds showing surface-activity. We have found that if solvent-soluble resins are prepared from difunctional direactive) phenols in which one of the reactive (0 or p) positions of the phenol is substituted by a hydrocarbon radical having 4- to 12 carbon atoms, in the substantial absence of trifunctional phenols, and aldehydes having not over 8 carbon atoms, subsequent oxyalkylation, and specifically oxyethylation, yields products of unusual value for demulsification purposes, provided that oxyalkylation is continued to the degree that hydrophile properties are imparted to the compound. By substantial absence of trifunctional phenols," we mean that such materials may be present only in amounts so small that they do not interfere with the formation of a solvent-soluble resin product and, especially, of a hydrophile oxyalkylated derivative thereof. The actual amounts to be tolerated will, of course, vary with the nature of the other components of the system; but in general the proportion of trifunctional phenols which is tolerable in the conventional 'resinification procedures illustrated herein is quite small. In experiments following conventional procedure using an acid catalyst in which we have included trifunctional phenols in amounts of from 3% to about 1% or somewhat less, based on the difunctional phenols, we have encountered difficulties in preparing oxyalkylated derivatives of the type useful in the practice of this invention.

Such products are rarely a single chemical compound but are almost invariably a mixture of cogeners. One useful type of compound may be exemplified in an idealized simplification in the following formula:

omlniown' owlmown mounmbn H I g C H H R R n" It which, in turn, is considered a derivative of the fusible, organic solvent-soluble resin polymer the parent resin is fusible and organic solventsoluble; n represents a numeral varying from 1 to 20, with the proviso that the average value of n be at least 2; and R is a hydrocarbon radical having at least 4 and not over 12 carbon atoms. These numerical values of n and n" are, of course, on a statistical basis.

The present invention involves the use, as a demulsifier, of a hydrophile oxyalkylated 2, 4, 6 (i. e., 2, 4 or 6) C4- to Ciz-hydrocarbon substituted monocyclic pheno1C2- to Caaldehyde resin in which the ratio of oxyalkylene groups to phenolic nuclei is at least 2:1 and the alkylene radicals of the oxyalkylene groups are ethylene, propylene, butylene, hydroxypropylene or hydroxybutylene corresponding to the alpha-beta alkylene oxides, ethylene oxide, alpha-beta propylene oxide, alpha-beta butylene oxide, glycide and methyl glycide.

More particularly the present invention involves the use, as a demulsifier, of a compound having the following characteristics:

(1) Essentially a polymer, probably linear but not necessarily so, having at least 3 and preferably not over 15 or 20 phenolic or structural units. It may have more, as previously stated.

(2) The parent resin polymer being fusible and organic solvent-soluble as hereinafter described.

(3) The parent resin polymer being free from cross-linking, or structure which cross-links during the heating incident to the oxyalkylation procedure to an extent sufficient to prevent the possession of hydrophile or sub-surface-active or surface-active properties by the oxyalkylated resin. Minor proportions of trifunctional phenols sometimes present in commercial difunctional phenols are usually harmless.

(4) Each alkyleneoxy group is introduced at the phenolic hydroxyl position except possibly in an exceptional instance where a stable methylol group has been formed by virtue of resin manufacture in presence of an alkaline catalyst. Such occurrence of a stable methylol radical is the exception rather than the rule, and in any event apparently does not occur when the resin is manufactured in the presence of an acid catalyst.

(5) The total number of alkyleneoxy radicals introduced must be at least equal to twice the phenolic nuclei.

(6) The number of alkyleneoxy radicals introduced not only must meet the minimum of item (5) above but must be sufficient to endow the product with sufficient hydrophile property to have emulsifying properties, or be self-emulsifiable or self-dispersible, or the equivalent as hereinafter described. The invention is concerned particularly with the use of sub-surface-active and surface-active compounds.

(7) The use of a product derived from a parasubstituted phenol is advantageous as compared with the use of a product derived from an orthosubstituted phenol, when both are available. This preference is based in part on the fact that the para-substituted phenol is usually cheaper, and also where we have been able to make a com- 1 parison it appearsto be definitely better, in improving the effectiveness of demulsifiers.

We have found when oxyalkylated derivatives are obtained conforming to the above specifications, particularly in light of what is said hereinafter in greater detail, that they have unusual properties which can be better understood perhaps in light of the following:

(a) The property is not uniformly inherent in every analogous structure for the reason that if the methylene group is replaced by sulfur, for example, we have found such compounds to be of lesser value.

(b) Similarly, the property is not uniformly inherent in every analogous structure for the reason that if R is replaced by some other substituent, for instance chlorine, the compounds obtained are of a reduced value in comparison with the outstanding compounds derived, for example, from difunctional butylphenol, difunctional amylphenol, difunctional octylphenol, difunctional menthyl phenol, difunctional dodecyl phenol, difunctional nonyl phenol, etc.

(0) We know of no theoretical explanation of the unusual properties of this particular class of compounds and, as a matter of fact, wehave not been able to find a satisfactory explanation even after we have prepared and studied several hundred typical compounds.

We have also found that the remarkable properties of the parent materials as demulsifiers persist in derivatives which bear a simple genetic relationship to the parent material, and in fact to the ultimate resin polymer, for instance, in the products obtained by reaction of the oxyalkylated compounds with low molal monocarboxy acids, high molal monocarboxy acids, polycarboxy acids or their anhydrides, alpha-chloro monocarboxy acids, epichlorohydrin, etc. The derivatives also preferably must be obtained from oxyalkylated products showing at least the necessary hydrophile properties per se.

As previously stated, the present invention is concerned primarily with the resolution of petroleum emulsions of the water-in-oil type by means of certain specified demulsifiers. The specified demulsifiers are the products obtained by the oxyalkylation of certain resins, which in turn are derived by chemical reaction between difunctional monohydric phenols and a reactive aldehyde such as formaldehyde, nearby homologues, and their equivalents. The phenolic reactant is characterized by one ortho-para. nuclear hydrocarbon substituent having not less than 4 carbon atoms and not more than. 12 carbon atoms. Usually the phenolic reactants are derivatives of hydroxybenzene, i. e., ordinary phenol, and are usually obtained by reaction of phenol with an olefin or an organic chloride in presence of a metallic halide or condensing agent, but similar phenolic reactants obtained from metacresol or 3,5-xylenol are equally satisfactory for the reason that such phenols are still difunctional (dlreactive) and the presence of the single or even both methyl radicals does not materially affect the sub-surface-activity or the surface-activity or hydrophile balance. The hydrocarbon substituent having 4 to 12 carbon atoms may be alkyl, alkylene, aryl, alicyclic or aralkyl.

Any aldehyde capable of forming a methylol or a substituted methylol group and having not more than 8 carbon atoms is satisfactory, so long as it does not possess some other functional group or structure which will conflict with the resinification reaction or with the subsequent oxyalkylation of the resin, but the use of formaldehyde, in its cheapest form of an aqueous solution, for the production of the resins is particularly advantageous. Solid polymers of formaldehyde are more expensive and higher aldehydes are both less reactive, and are more expensive. Furthermore, the higher aldehydes may undergo other reactions which are not desirable, thus introducing difilculties into the resinification step. Thus acetaldehyde, for example, may undergo an aldol condensation, and it and most of the higher aldehydes enter into self-resinfication when treated with strong acids or alkalis. On the other hand, higher aldehydes frequently beneficially affect the solubility and fusibility of a resin. This is illustrated, for example, by the different characteristics of the resin prepared from paratertiary 'amyl phenol and formaldehyde on one hand and a comparable product prepared from the same phenolic reactant and heptaldehyde on the other hand. The former, as shown in certain subsequent examples, is a hard, brittle solid, whereas the latter is soft and tacky, and obviously easier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. The employment of furfural requires careful control for the reason that in addition to its aldehydic function, furfural can form vinyl condensations by virtue of its unsaturated structure. The production of resins from furfural for use in preparing products for the present process is most conveniently conducted with weak alkaline catalysts and often with alkali metal carbonates. Useful aldehydes, in addition to formaldehyde, are acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, ethylbutyraldehyde, heptaldehyde, and benzaldehyde, furfural and glyoxal. It would appear that the use of glyoxal should be avoided due to the fact that it is tetrafunctional. However, our experience has been that, in resin manufacture and particularly as described herein, apparently only one of the aldehydic functions enters into the resinif'lcation reaction. The inability of the other aldehydic function to enter into the reaction is presumably due to steric hindrance; Needless to say, one can use a. mixture of two or more aldehydes although usually this has no advantage.

Resins of the kind which are used as intermediates for the compounds used in the practice of this invention are obtained with the use of acid catalysts or alkaline catalysts, or without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines, and quaternary ammonium bases. It is generally accepted that when ammonia and amines are employed as catalysts they enter into the condensation reaction and, in fact, may operate by initial combination with the aldehydic reactant. The compound hexamethylenetetramine illustrates such a combination. In light of these various reactions it becomes difficult to present any formula which would depict the structure of the various resins prior to oxyalkylation. More will be said subsequently as to the difference between the use of an alkaline catalyst and an acid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the products are not identical where different basic materials are employed. The basic materials employed include not only those previously enumerated but also the hydroxides of the alkali metals, hydroxides of the alkaline earth metals, salts of strong bases and weak acids such as sodium acetate, etc.

Suitable phenolic reactants include the following: Para-tertiary butyphenol; para-secondary butylphenol; para tertiary amylphenol; para secondary amylphenol; para tertiaryhexylphenol; para-isooctylphenol; ortho-phenylphenol; para-phenylphenol; ortho -benzylphenol; para benzylphenol; para cyclohexylphenol; para-decyl-phenol; para-dodecyl-phenol; paranonyl-phenol; para-menthyl-phenol; parabetanaphthyl-phenol; para-alpha-naphthyl-phenol: para-cumyl-phenol; phenols of the formula in which R1 represents a straight chain hydrocarbon radical containing at least 7 carbon atoms and R2 and R3 represent hydrocarbon radicals, the total number of carbon atoms attached to the tertiary carbon being 11; and phenols of the formula in which R1 represents an alkyl hydrocarbon radical containing at least 7 carbon atoms and R2 represents an alkyl hydrocarbon radical containing at least 2 carbon atoms, the total number of carbon atoms in R1 and R2 being 11; and the corresponding ortho-para substituted metacresols and 3,5-xylenols.

For convenience, the phenol has previously been referred to as monocyclic in order to differentiate from fused nucleus polycyclic phenols, such as substituted naphthols. Specifically, monocyclic is limited to the nucleus in which the hydroxyl radical is attached. Broadly speaking, where a substituent is cyclic, particularly aryl, obviously in the usual sense such phenol is actually polycyclic although th phenolic hydroxyl is not attached to a fused polycyclic nucleus. Stated another way, phenols in which the hydroxyl group is directly attached to a condensed or fused polycyclic structure, are excluded. This matter, however, is clarified by the following consideration. The phenols here in contemplated for reaction may be indicated by the following formula:

in which R is selected from the class consisting of hydrogen atoms and hydrocarbon radicals having at least 4 carbon atoms and not more than 12 carbon atoms, with the proviso that one occurrence of R is the hydrocarbon substituent and the other two occurrences are hydrogen atoms, and with the further provision that one or both of the 3 and 5 positions may be methyl substituted. v

The above formula possibly can be restated more convenientlyin the following manner, to wit, that the phenol employed is of the following formula, with the proviso that R is a hydrocarbon substituent located in the 2,4,6 position, again with the provision as to 3 or 3,5 methyl substitu tion. This is conventional nomenclature, numbering the various positions in the usual clockwise r 7 manner, beginning with the hydroxy position as one:

The manufacture of thermoplastic phenolaldehyde resins, particularly from formaldehyde and a difunctional phenol, i. e., a phenol in which one of the three reactive positions (2,4,6) has been substituted by a hydrocarbon group, and

particularly by one having at least 4 carbon atoms and not more than 12 carbon atoms, is well known. As has been previously pointed out, there is no objection to a methyl radical provided it is present in the 3 or position.

Thermoplastic or fusible phenol-aldehyde resins are usuall manufactured for the varnish trade and oil solubility is of prime importance. For this reason, the common reactants employed are butylated phenols, amylated phenols, phenylphenols, etc. The methods employed in manufacturing such resins are similar to those employed in the manufacture of ordinary phenolformaldehyde resins, in that either an acid or alkaline catalyst is usually employed. The procedure usually differs from that employed in the manufacture of ordinary phenol-aldehyde resins in that phenol, being water-soluble, reacts readily with an aqueous aldehyde solution without further difficulty, While when a water-insoluble phenol is employed some modification is usuall adopted to increase the interfacial surface and thus cause reaction to take place. A common solvent is sometimes employed. Another procedure employs rather severe agitation to create a large interfacial area. action starts to a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass and assist in hastening the reaction. We have found it desirable to employ a small proportion of an organic sulfo-acid as a catalyst, either alone or along with a mineral acid like sulfuric or hydrochloric acid. For example, alkylated aromatic sulfonic acids are effectively employed. Since commercial formsof such acids are commonly their alkali salts, it is sometimes convenient to use a small quantity of such alkali salt plus a small quantity of strong mineral acid, as shown in the examples below. If desired, such organic sulfo-acids may be prepared in situ in the phenol employed, by reacting concentrated sulfuric acid with a small proportion of the phenol. In such cases where xylene is used as a solvent and concentrated sulfuric acid is employed, some sulfonation of the xylene probably occurs to produce the sulfo-acid. Addition of a solvent such as xylene is advantageous as hereinafter described in detail. Another variation of procedure is to employ such organic sulfo-acids, in the form of their salts, in connection with an alkali-catalyzed resinification procedure. Detailed examples are included subsequently.

Another advantage in the manufacture of the thermoplastic or fusible type of resin by the acid catalytic procedure is that, since a difunctional phenol is employed, an excess of an aldehyde, for instance formaldehyde, may be employed without too marked a change in conditions of reaction and ultimate product. There is usually little, if any, advantage, however, in using an excess over and above the stoichiometric proportions for the reason that such excess may be lost Once the reand wasted. For all practical purposes the molar ratio of formaldehyde to phenol may be limited to 0.9 to 1.2, with 1.05 as the preferred ratio, or sufficient, at least theoretically, to convert the remaining reactive hydrogen atom of each terminal phenolic nucleus. Sometimes when higher aldehydes are used an excess of aldehydic reactant can be distilled oil and thus recovered from the reaction mass. This same procedure may be used with formaldehyde and excess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularly formaldehyde, may be increased over the simple stoichiometric ratio of one-to-one or thereabouts'. With the use of alkaline catalyst it has been recognized that considerably increased amounts of formaldehyde may be used, as much as two moles of formaldehyde, for example, per mole of phenol, or even more, with the result that only a small part of such aldehyde remains uncombined or is subsequently liberated during resinification. Structures which have been advanced to explain such increased use of aldehydes are the following:

Such structures may lead to the production of cyclic polymers instead of linear polymers. For this reason, it has been previously pointed out that, although linear polymers have by far the most important significance, the present invention does not exclude resins of such cyclic structures.

Sometimes conventional resinification procedure is employed using either acid or alkaline catalysts to produce low-stage resins. Such resins may be employed as such, or may be altered or converted into high-stage resins, or in any event, into resins of higher molecular weight, by heating along with the employment of vacuum so as to split oil water or formaldehyde, or both. Generally speaking, temperatures employed, particularly with vacuum, may be in the neighborhood of to 250 C., or thereabouts.

It may be well to point out, however, that the amount of formaldehyde used may and does usually aflect the length of the resin chain. Increasing the amount of the aldehyde, such as formaldehyde, usually increases the size or molecular weight of the ploymer.

In the hereto appended claims there is specified, among other things, the resin polymer containing at least 3 phenolic nuclei. Such minimum molecular size is most conveniently determined as a rule by cryoscopic method using benzene, or some other suitable solvent, for instance, one of those mentioned elsewhere herein as a solvent for such resins. As a matter of fact, using the procedures herein described or any conventional resinification procedure will yield products usually having definitely in excess of 3 nuclei. In other Words, a resin having an average of 4, 5 or 5 2 nuclei per unit is apt to be formed as a minimum in resinification, except under certain special conditions where dimerization may occur.

However, if resins are prepared at substantially higher temperatures, substituting cymene, tetralin, etc., or some other suitable solvent which boils or refiuxes at a higher temperature, instead of xylene, in subsequent examples, and if one doubles or triples the amount of catalyst, doubles or triples the time of refluxing, uses a marked excess of formaldehyde or other aldehyde, then the average size of the resin is apt to be distinctly over the above values, for example, it may average 7 to 15 units. Sometimes the expression lowstage resin or low-stage" intermediate is employed to mean a stage having 6 or '7 units or even less. In the appended claims we have used low-stage to mean 3 to 7 units based on average molecular weight.

The molecular weight determinations, of course, require that the product be completely soluble in the particular solvent selected as, for instance, benzene. The molecular weight determination of such solution may involve either the freezing point as in the cryoscopic method, or, less conveniently perhaps, the boiling point in an ebullioscopic method. The advantage of the ebullioscopic method is that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ is that of Menzies and Wright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suitable method for determining molecular weights will serve, although almost any procedure adopted has inherent limitations. A good method for determining the molecular weights of resins,

especially solvent-soluble resins, is the cryoscopic procedure of Krumbhaar which employs diphenylamine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co. 1947).

Subsequent examples will illustrate the use of an acid catalyst, an alkaline catalyst, and no catalyst. As far as resin manufacture per se is concerned, we prefer to use an acid catalyst, and particularly a mixture of an organic sulfoacid and a mineral acid, along with a suitable solvent, such as xylene, as hereinafter illustrated in detail. However, we have obtained products from resins obtained by use of an alkaline catalyst which were just as satisfactory as those obtained employing acid catalysts. Sometimes a combination of both types of catalysts is used in difierent stages of resinification. Resins so obtained are also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., those referred to as highstage resins, are conveniently obtained by subjecting lower molecular weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a modest amount or even perhaps no low polymer, yet it is almost certain to produce further polymerization. For instance, acid catalyzed resins obtained in the usual manner and having a molecular weight ind cating the presence of approximately 4 phenolic units or thereabouts may be subjected to such treatment. with the result that one obtains a resin having approximately double this molecular weight. The usual procedure is to use a secondary step, heating the resin in the presence (1' absence of an inert gas, including steam, or by we of vacuum.

While under the usual conditions of resinificalion employing difunctional phenols, there is little or no tendency to form binuclear compounds,

i. e., dimers. resulting from the combination, for example, of two mols of a phenol and one mol of formaldehyde, where the substituent which 10 makes the phenol dii'unctional has not more than 4 or 5 carbon atoms. with phenols in which the ortho or para-substituent approximates the upper limit specified herein, for instance, 10 or 12, there is an increased tendency to form a measurable amount of dimers. This formation of a measurable but nevertheless relatively small amount of dimers is unimportant and there is no reason to separate the dimers prior to oxyalkylation and use. Substituted dihydroxydiphenylmethanes obtained from substituted phenols are not resins as that term is used herein.

Although any conventional procedure ordinarily employed. may be used in the manufacture of the herein contemplated resins or, for that matter, such resins may be purchased in the open market, we have found it particularly desirable to use the'procedures described elsewhere herein, and ernploying a combination of an organic sulfo-acid and a mineral acid as a catalyst, and xylene as a solvent. By way of illustration, certain subsequent examples are included, but it is to be understood the herein described invention is not concerned with the resins per 'se or with any particular method of manufacture but is concerned with the use of derivatives obtained by the subsequent oxyalkylation thereof. The phenol-aldehyde resins may be prepared in any suitable manner.

oxyalkylation, particularly oxyethylation which is the preferred reaction, depends on contact between a non-gaseous phase and a gaseous phase.

an inert solvent such as xylene.

It can, be example, be carried out by melting the thermoplastic resin and sub ecting it to treatment with ethylene oxide or the like, or by treating a suitable solution or suspension. Since the melting points of the resins areoften higher than desired in the inital stage of oxyethylation, we have found it advantageous to use a solution or suspension of thermoplastic resin in Under such circumstances, the resin obtained in the usual manner is dissolved by heating in xylene under a reflux condenser or in any other suitable manner. Since xylene or an equivalent inert solvent is present or may be present during oxyalkylation, it is obvious there is no objection to having a solvent present during the resinifying stage if, in addition to being inert towards the resin, it is also inert towards the reactants and also inert towards water. Numerous solvents. particularly of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl benzene, propyl benzene, mesitylene, decalin (decahydronaphthalene) tetralin (tetrahydronaphthalene) ethylene glycol diethylether, diethylene glycol diethylether, and tetraethylene glycol dimethylether. or mixtures of one or more. Solvents such as dichloroethylether, or dichloropropylether may be employed either alone or in mixture but have the objection that the chlorine atom in the compound may slowly combine with the alkaline catalyst employed in oxyethylation. Suitable solvents may be selected from this group for molecular weight determinations.

The use of such solvents is .1 convenient expedient in the manufacture of the thermoplastic resins, particularly since the solvent gives a more liquid reaction mass and thus prevents overheating, and also because the solvent can be employed in connection with a reflux condenser and a water trap to assist inthe removal of water of reaction and also-water present as part of the formaldehyde reactant when an aqueous solution of formaldehyde is used. Such aqueous solution, of course, with the ordinary product of commerce containing about 37 to 40% formaldehyde, is the preferred reactant. When such solvent is used it is advantageously added at the beginning of the resinificatlon procedure or before the reaction has proceeded very far.

The solvent can be removed afterwards by distillation with or without the use of vacuum, and a final higher temperature can be employed to complete reaction if desired. In many instances it is most desirable to permit part of the solvent, particularly when it is inexpensive, e. g., xylene, to remain behind in a predetermined amount so as to have a resin which can be handled more conveniently in the oxyalkylation stage. If a more expensive solvent, such as decalin, is employed, xylene or other inexpensive solvent may be added after the removal of decalin, if desired.

In preparing resins from difunctional phenols it is common to employ reactants of technical grade. The substituted phenols herein contemplated are usually derived from hydroxybenzene. As a rule, such substituted phenols are comparatively free from unsubstituted phenol. We have generally found that the amount present is considerably less than 1% and not infrequently in the neighborhood of of 1%, or even less. The amount of the usual trifunctional phenol, such as hydroxybenzene or metacresol, whichcan be tolerated is determined by the fact that actual crosslinking, if it takes place even infrequently, must not be sumcient to cause insolubility at the completion of the resini-fication stage or the lack of hydrophile properties at the completion of the oxyalkylation stage;

The exclusion of such trifunctional phenols as,

available or having a. hydroxymethyl or a sub-v stituted hydroxymethyl group present is a po tential source of cross-linking either during resinification or oxyalkylatlon. Cross-linking leads either to insoluble resins or to non-hydrophilic in the resins, or that the product resulting from oxyalkylation is gelatinous, rubbery, or at least not hydrophilen As to the rationale of resinification, note particularly what is said hereafter in dliferentiating between resoles, novolaks, and resins obtained solely from difunctional phenols.

It should be noted that where the substituent has 9 to 12 carbon atoms, as in certain of the phenols used in preparing the products used in accordance with the present invention, the tolerance for trifunctional phenols is substantially greater than it is with phenols in which the substituent is a lower hydrocarbon group.

Previous reference has been made to the fact that fusible organic solvent-soluble resins are usually linear but may be cyclic. Such more complicated structure may be formed, particularly.

if a resin prepared in the usual manner is converted into a higher stage resin by heat treatment in vacuum as previously mentioned. This again is a reason for avoiding any opportunity for cross-linking due to the presence of any appreciable amount of trifunctional phenol. In other words, the presence of such reactant may cause cross-linking in a convention resiniilca tion procedure, or in the oxyalkylation procedure, or in the heat and vacuum treatment if it is employed as part of resin manufacture.

Our routine procedure in examining a phenol for suitability for preparing products to be used in practicing the invention is to prepare a resin employing formaldehyde in excess (1.2 moles of formaldehyde per. mole of phenol) and using an -acid catalyst in the manner described hereinafter in Example 1a. If the resin so obtained is solvent-soluble in any one of the aromatic or other solvents previously referred to, it is then subjected to oxyethylation. During oxyethylation a temperature is employed of approximately to C. with addition of at least 2 and advantageously up to 5 moles of ethylene oxide per phenolic hydroxyl. The oxyethylation is advantageously conducted so as to require froma few minutes up to 5 to 10 hours. If the product so obtained is solvent-soluble and self-dispersing or emulsifiable, or has emulsifying properties, the phenol is perfectly satisfactory from the standpoint of trifunctional phenol content. The solvent may be removed prior to the dispersibility or emulsiflability test. When a product becomes rubbery during oxyalkylation due to the presence of a small amount of trireactive phenol, as previously mentioned, or for some other reason, it may become extremely insoluble, and no longer qualifies as being hydrophile as herein specified. Increasing the size of the aldehydic nucleus, for instance using heptaldehyde instead of formaldehyde, increases tolerance for trifunctional phenol.

The presence of a trifunctional or tetrafunctional phenol (such as resorcinol or bisphenol A) is apt to produce detectable cross-linking and insolubilization but will not necessarily do so, especially if the proportion is small. Resiniflcation involving difunctional phenols only may also produce insolubilization, although this seems to be an anomaly or a contradiction of what is sometimes said in regard to resinification reactions involving difunctional phenols only. This is presumably due to cross-linking. This appears to be contradictory to what one might expect in light of the theory of functionality in resinification. It is true that under ordinary circumstances, or rather under the circumstances of conventional resin manufacture, the procedures employing difunctional phenols are very apt to, and almost invariably do, yield solvent-soluble, fusible resins. However, when conventionalprocedures are employed in connection with resins for varnish manufacture or the like, there is involved the matter of color, solubility in oil, etc. when resins of the same type are manufactured for the herein contemplated purpose, 1. e., as a raw material to be subjected to oxyalkylation, such criteria of selection are no longer pertinent.

Stated another way, one may use more drastic conditions of resiniflcation than those ordinarily employed to" produce resins for the present purposes. Such more drastic conditions of resinification may include increased amounts of catalyst, higher temperatures, longer time of reaction, subsequent reaction involving heat alone or in combination with vacuum, etc. Therefore, one is not only concerned with the resinification reactions which yield the bulk of ordinary resins from alkaline catalyst.

difunctional phenols but also and particularly with the minor reactions of ordinary resin manufacture which are of importance in the present invention for the reason that they occur under more drastic conditions of resinification which may be employed advantageously at times, and they may lead to cross-linking.

In this connection it may be well to point out that part of these reactions are now understood or explainable to a greater or lesser degree in light of a most recent investigation. Reference is made to the researches of Zinke and his coworkers. Hultzsch and his associates, and to von Eulen and his co-workers, and others. At to a bibliography of such investigations, see Carswell, Phenoplasts, chapter 2. These investigators limited much of their work to reactions involving phenols having two or less reactive hydrogen atoms. Much of what appears in these most recent and most up-to-date investigations is pertinent to the present invention insofar that much of it is referring to resinification involving difunctional phenols.

For the moment, it may be simpler to consider a "most typical type of fusible resin and forget for the time that such resin, at least under certain circumstances, is susceptible to further complications. Subsequently in the text it will be pointed out that cross-linking or reaction with excess formaldehyde may take place even with one of such most typical type" resins. This point is made for the reason that insolubles must be avoided in order to obtain the products herein contemplated for use as demulsifying agents.

The "typical type of fusible resin obtained from a para-blocked or ortho-blocked phenol is clearly differentiated from the Novolak type or resole type of resin. Unlike the resole type, such "typical type" para-blocked or ortho-blocked phenol resin may be heated indefinitely without passing into an infusible stage, and in this respect is similar to a Novolak. Unlike the Novolak type the addition of a further reactant, for instance, more aldehyde, does not ordinarily alter fusibility of the difunctional phenol-aldehyde type resin; but such addition to a Novolak causes cross-linking by virtue of the available third functional position.

What has been said immediately preceding is subject to modification in this respect: It is well known, for example, that difunctional phenols, for instance, paratertiaryamylphenol, and an aldehyde, particularly formaldehyde, may yield heat-hardenable resins, at least under certain conditions, as for example the use of two moles of formaldehyde to one of phenol, along with an This peculiar hardening or curing or cross-linking of resins obtained from difunctional phenols has been recognized by various authorities.

The compounds herein used must be hydrophile or sub-surface-active or surface-active as hereinafter described, and this precludes the formation of insolubles during resin manufacture or the subsequent stage of resin manufacture where heat alone, or heat and vacuum, are employed,

or in the oxyalkylation procedure. In its simplest presentation the rationale of resiniflcation involving formaldehyde, for example, and a difunctional phenol would not be expected to form cross-links. However, cross-linking sometimes occurs and it may reach the objectionable stage. However, provided that the preparation of resins simply takes into cognizance the present knowledge of the subject, and employing preliminary,

(ill

exploratory routine examinations as herein indicated, there is not the slightest difliculty in preparing a very large number of resins of various types and from various reactants, and by means of different catalysts by different procedures, all of which are eminently suitable for the herein described purpose.

Now returning to the thought that cross-linking can take place, even when difunctional phenols are used exclusively, attention is directed to the following: Somewhere during the course of resin manufacture there may be a potential cross-linking combination formed but actual cross-linking may not take place until the subsequent stage is reached, 1. e., heat and vacuum stage, or oxyalkylation stage. This situation may be related or explained in terms of a theory of flaws, or Lockerstellen, which is employed in explaining flaw-forming groups due to the fact that a CHzOH radical and H atom may not lie in the same plane in the manufacture of ordinary phenol-aldehyde resins.

Secondly, the formation or absence of formation of insolubles may be related to the aldehyde used and the ratio of aldehyde, particularly formaldehyde, insofar that a slight variation may, under circumstances not understandable, produce insolubilization. The formation of the insoluble resin is apparently very sensitive to the quantity of formaldehyde employed and a slight increase in the proportion of formaldehyde may lead to the formation of insoluble gel lumps. The cause of insoluble resin formation is not clear, and nothing is known as to the structure of these resins.

All that has been said previously herein as regards resinification has avoided the specific reference to activity of a methylene hydrogen atom. Actually there is a possib lity that under some drastic condit ons cross-linking may take place through formaldehyde addition to the methylene bridge. or some other reaction involving a methylene hydrogen atom.

Finally, there is some evidence that, although the meta positions are not ordinarily reactive, possibly at times methylol groups-or the l ke are formed at the meta positions; and if this were the case it may be a suitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instance formaldehyde, is not to be taken as a criterion of rejection for use as a reactant.

In other words, a phenol-aldehyde resin which is thermoplastic and solvent-soluble, particularly if xylene-soluble, is perfectly satisfactory even though retreatment with more aldehyde may change its characteristics markedly in regard to both fusibility and solubility. Stated another way, as far as resins obtained from difunctional phenols are concerned, they may be either formaldehyde-resistant or not formaldehyde-resistant.

Referring again to the resins herein contemplated as reactants, it is to be noted that they are thermoplastic phenol-aldehyde resins derived from difunctional phenols and are clearly distinguished from Novolaks or resoles. When these resins are produced from difunctional phenols and some of the higher alphatc aldehydes, such as acetaldehyde, the resultant is often a comparatively soft or pitchlike resin at ordinary temperature. Such resins become comparaiively fluid at to C. as a rule and thus can be readily oxyalkylated, preferably oxyethylated, Without the use of a solvent.

Reference has been made to the use of the word aseam "fusible. Ordinarily a thermoplastic resin is identified as one which can be heated repeatedly and still not lose its thermoplasticity. It is recognized, however, that one may have a resin which is initially thermoplastic but on repeated heating may become insoluble in an organic solvent, or at least no longer thermoplastic, due to the fact that certain changes take place very slowly. As far as the present invention is concerned, it isobvious that a resin to be suitable need only be sufliciently fusible to permit processing to produce our oxyalkylated products and not yield insolubles or cause insolubilization or gel formation, or rubberiness, as previously described. Thus resins which are, strictly speaking, fusible but not necessarily thermoplastic. in the most rigid sense that such terminology would be applied to the mechanical properties of a resin, are useful intermediates. The bulk of all fusible resins of the kind herein described are thermoplastic.

The fusible or thermoplastic resins, or solventsoluble resins, herein employed as reactants, are water-insoluble, or have no appreciable hydrophile properties. The hydrophile property is introduced by oxyalkylation. pended claims and elsewhere the expression water-insoluble" is used to point out this characteristic of the resins used.

In the manufacture of compounds herein employed, particularly for demulsiflcation, it is obvious that the resins can be obtained by one of a number of procedures. In the first place, suitable resins are marketed by a number of companies and can be purchased in the open market; in the second place, there are a wealth of examples of suitable resins described in the literature. The third procedure is to follow the directions of the present application.

The invention will be illustrated by the following specific examples, giving specific directions for preparing oxyalkylation-susceptible, water-insoluble, organic solvent-soluble, fusible phenol-aldehyde resins derived from difunctional phenols (Examples 111-10311) carrying out the oxyalkylation procedure to produce products useful in the practice of the invention (Examples 1b-18b and Table) and using the products for demulsification (Examples 1c-5c), but it is not limited thereto.

Example In Grams Para-tertiary butylphenol (1.0 mole) 150 Formaldehyde 37% (1.0 mole) 81 Concentrated HCl 1.5

Monoalkyl (Clo-C20, principally Cu -C14) benzene monosulfonic acid sodium salt 0.8 xylene 100 (Examples of alkylaryl sulfonic acids which serve as catalysts and as emulsifiers particularly in the form of sodium salts include the following:

R is an alkyl hydrocarbon radical having 12-14 carbon atoms.

In the hereto ap- I 10 2, in such instances where R. contains less than 8 carbon atoms.

With respect to alkylaryl sulfonic acids or the sodium salts, we have employed a monoalkylated benzene monosulfonic acid or the sodium salt thereof wherein the alkyl group contains 10 to 14 carbon atoms. We have found equally effective and interchangeable the following specific sulfonic acids or their sodium salts: A mixture of diand tripropylated naphthalene monosulfonic acid; diamylated naphthalene monosulfonic acid; and nonyl naphthalene monosulfonic acid.)

The equipment used was a conventional twopiece laboratory resin pot. The cover part of the equipment had four openings: One for reflux condenser; one for the stirring device; one for a separatory funnel or other means of adding reactants; and a thermometer well. In the manipulation employed, the separatory funnel insert for adding reactants was not used. The device was equipped with a. combination-reflux and water-trap apparatus so that the single piece of apparatus could be used as either a reflux condenser or a water trap, depending on the position of the three-way glass stopcock. This permitted convenient withdrawal of water from the water trap. The equipment, furthermore, permitted any setting of the valve without disconnecting the equipment. The resin pot was heated with a glass fiber electrical heater constructed to fit snugly around the resin pot. Such heaters, with regulators, are readily available.

The phenol, formaldehyde, acid catalyst, and solvent were combined in the resin pot above described. This particular phenol was in the form of a flaked solid. Heat .was applied with gentle stirring and the temperature was raised to 80-85 C., at which point a mild exothermic react. m took place. This reaction raised the temperature to approximately -110 C. The reaction mixture was then permitted to reflux at 100-105 C. for between one and one and one-half hours. The reflux trap arrangement was then changed from the reflux position to tlz'; normal water entrapment position. The water of solution and the water of reaction were permitted to distill out and collect in the trap. As the water distilled out, the temperature gradually increased to approximately C. which required between 1.5 to 2 hours. At this point the water recovered in the trap, after making allowance for a small amount of water held up in the solvent, corresponded to the expected quantity.

The solvent solution so obtained was used as such in subsequent oxyalkylation steps. We have also removed the solvent by conventional means, such as evaporation, distillation or vacuum distillation, and we customarily take a small sample of the solvent solution and evaporate the solvent to note the characteristics of the solvent-free resin. The resin obtained in the operation above described was clear, light amber colored, hard, brittle, and had a melting point of -165 C.

Attention is directed to the fact that tertiary butylphenol, in presence of a strong mineral acid as a catalyst and using formaldehyde, sometimes yields a resin which apparently has a very slight amount of cross-linking. Such resin is similar to the one described above except that it is somewhat opaque, and its melting point is higher than the one described above and there is a tendency to cure. Such a resin is generally dispersible in xylenebut not soluble to give a clear solution. Such dispersion can be oxyalkylated in the same manner as the clear resin. If desired, a minor proportion of another and inert solvent, such as diethyleneglycol diethylether, may be employed along with xylene, to give a clear solution prior to oxyalkylation. This fact of solubilization shows the present resin molecules are still quite small, as contrasted with the very large size of extensively cross-linked resin molecules. If following a given procedure with a given lot of the phenol, such a resin is obtained, the amount of catalyst employed is advantageously reduced slightly or the time of reflux reduced slightly, or both, or an acid such as oxalic acid is used instead of hydrochloric acid. Purely as a matter of convenience due to better solubility in xylene, we prefer to use a clear resin but if desired either type may be employed.

Example 2a somewhat opaque but completely xylene-soluble.

It was semi-soft or pliable in consistency. See what is said in Example 1a, preceding, in'regard to the opaque appearance of the resin. What is said there applies with equal force and effect in the instant example.

Example 3a Grams- Para-tertiary amylphenol (1.0 mole) 164 Formaldehyde 37% (1.0 mole) 81 HCl (concentrated) 1.5

Monoalkyl (Cm-C20, principally 012-014) benzene monosulfonic acid sodium salt 0.8 Xylene 100 The procedure followed was the same as that used in Example 1a, preceding. The phenol employed was a flaked solid. The solvent-free resin was dark red in color, hard, brittle, with a melting point of 128-140" C. It was xylene-soluble.

Example 4a The phenol employed (164 grams) was parasecondary amylphenol, which is liquid. The procedure followed was the same as that used in Example 1a, preceding. The solvent-free resin was hard and brittle, reddish-black in color and r with a melting point of 8085 C.

Example 5a The phenol employed (164 grams) was a commercially available mixed amylphenol containing approximately 95 parts of para-tertiary amylphenol, and 5 parts of ortho-tertiary amylphenol. It was in the form of a fused solid. The procedure employed was the same as that used in Example 1a, preceding. The appearance of the resin was substantially the same as that of the product of Example 3a.

Sometimes resins produced from-para-tertiary amylphenol and formaldehyde in the presence of an acid catalyst show a slight insolubility in xylene; that is, while completely soluble in hot xylene to give a clear solution they give a turbid solution in cold xylene. Such turbidity or lack of solubility disappears on heating, or on the addition of diethylethyleneglycol.

(5 ing in the neighborhood of 150 C. or thereabouts.

We have never noticed this characteristic property when using the commercial phenol of Example 5a which, as stated, is a mixture containing para-tertiary amylphenol and 5% ortho-tertiary amylphenol. In fact, the addition of 5% to 8% of an ortho-substituted phenol, such as ortho-tertiary amylphenol to any difunctional phenol, such as the conventional parasubstituted phenols herein mentioned, usually gives an increase in solubility when the resulting resin is high melting, which is often the case when formaldehyde and an acid catalyst are employed.

Example 611 The phenol employed (164 grams) was orthotertiary amylphenol which is a liquid. The procedure followed was the same as that used in Example 1a, and the appearance of the resin was light amber in color and transparent. It was soft to pliable in consistency and xylene-soluble.

Example 70 The phenol employed (178 grams) was para- Example 8a The phenol employed was commercial paraoctylphenol. 206 grams of this phenol were employed instead of 164 grams of an amylphenol or grams of a butylphenol and 150 grams of xylene were used instead of 100. Otherwise, the procedure was the same as that used in Example 1a. The solvent-free resin obtained was reddishamber in color, soft to pliable in consistency, and xylene-soluble.

' Example 9a Grams Para-phenylphenol "Q.

Diethyleneglycol diethylether 50 This phenol was solid. The phenol, xylene, diethyleneglycol diethylether, and hydrochloric acid were mixed together and heated to give complete solution at approximately 140 C. The use of diethyleneglycol diethylether, or some equivalent solvent, was necessary for the reason that this particular phenol is not sufficiently soluble in xylene. Having obtained a complete solution in the manner indicated, it was allowed to cool to approximately 75-80 C. and, thereafter, formaldehyde was added and the procedure was the same as that used in Example 1a.

The final product contained not only xylene but also diethyleneglycol diethylether. Since this latter does not distill out readily (boiling point 189 C.) we did not obtain a solvent-free resin sample but used the product as such for oxyethylation. As pointed out elsewhere, the presence of a solvent is usually desirable in the oxyalkylation step. We have, however, examined a number of para-phenylphenol-formaldehyde acid-catalyzed resins which were hard, brittle resins, and melt- When ortho-hydroxydiphenyl is substituted for para-hydroxydiphenyl one can eliminate the diethyleneglycol diethylether and use the procedure described in Example 1a, without modification. Ortho-substituted phenols yield resins which have lower melting points than do the para-substituted phenols and are usually more xylenesoluble than resins obtained from the corresponding para-substituted phenols. The matter of the lower melting point is also illustrated in the case of para-tertiary amylphenol resins in comparison with ortho-tertiary amylphenol resins. The resin obtained from ortho derivative and formaldehyde melts at about 80 C. and upward, whereas the comparable para. derivative resin melts at about 160 C. In this instance, both resins are xylene-soluble. Example a The same procedure was employed as in Example la, except that para-cyclohexylphenol, 1'76 grams, was employed along with 150 grams of xylene, This phenol was solid. The resulting resin minus solvents was opaque in appearance, xylene dispersible, amber in color, hard and brittle, with an approximate melting point of 170 C. It was sumciently curable so as to prohibit distillation.

Example 110 The same procedure was employed as in Example 1a, preceding, using 198 grams of commercial styrylphenol and 150 grams of xylene. Styrylphenol is a white solid. The resin was reddish black in color, hard and brittle, with a melting point of about 80 to 85 C.

Example 12a Grams Para-tertiary amylphenol (1.0 mole) 164 Formaldehyde 37% (0.8 mole) 64.8 Glyoxal 30% (0.1 mole) 20.0 Concentrated 'HCl 2 Monoalkyl (Cm-C20, principally Cir-C14) benzene monosulfonic acid sodium salt .75 Xylene 150 Example 13a i Grams Para-tertiary amylphenol (1.0 mole) 164 Glyoxal 30.2% (0.5 mole) 96 Concentrated HCl 2 Monoalkyl (Clo-C20, principally Cir-C14) monosulfonic acid sodium salt .8 Xylene 150 The same procedure was followed as in Example 1a. There was a modest precipitate of an insoluble material, approximately 15 grams, which had an insoluble sponge-like carbonaceous appearance. It was removed by filtration of the xylene solution as in'Example 12a preceding.-

The resulting solvent-free resin was clear, reddish amber incolor, solt to fluid in consistency, and xylene-soluble.

to add this amount of dfluted aldehyde.

The phenol, acid catalyst, and 50 grams of the xylene were combined in the resin pot previously described under Example In. The initial mixture did not include the aldehyde. The mixture was heated with stirring to approximately 150 C. and permitted to reflux.

The remainder of the xylene, 50 grams, was then mixed with the acetaldehyde; and this mixture was added slowly to the materials in the resin pot, with constant stirring, by means of the separatory funnel arrangement previously mentioned in the description of the resin pot in Example 1a. Approximately 30 minutes were required A mild exothermic reaction was noted at the first addition of the aldehyde. The temperature slowly dropped, as water of reaction formed, to about to C., with the reflux temperature being determined by the boiling point of water. After all the aldehyde had been added, the reactants were permitted to reflux for between an hour to an hour and a half before removing the water by means of the trap arrangement. After the water was removed the remainder of the procedure was essentially the same as in Example 1a. When a sample of the resin was freed from the solvent, it was dark red, semi-hard or pliable in consistency, and xylene-soluble.

Example 15a Example 16!! The same procedure was followed as in Example 14a, except that the grams of paratertiary butylphenol were replaced by 164 grams of para-tertiary amylphenol. The final solventfree resin was clear and dark red in color. It was xylene-soluble and semi-hard or pliable in consistency.

Example 17a The same procedure was followed as in Example 16a preceding except that the para-tertiary amylphenol was replaced .by an equal amount of para-secondary amylphenol. The appearance of the resin was substantially identical with that of the resin of the preceding example, except that it was somewhat more fiuid in consistency and slightly tacky.

' Example 18a The same procedure was followed as in Example 16a except that the amlyphenol employed was the phenol described in Example 5a. The appearance of the resin on a'solvent-free basis was substantially the same as that of Example Example 19a I The same procedure was followedas' in Example 16a except that the amylphenol employed was ortho-tertiary amylphenol. The resin on a The same procedure was followed as in Example 14a, except that the 150 grams of paratertiary butylphenol were replaced by 206 grams of-commercial para-octylphenol. The solvent-- free resin was dark red in color, soft to tacky in consistency, and xylene-soluble.

Example 21a The same procedure was employed as in Example 1441, except that the 150 grams of paratertiary butylphenol were replaced by 1'70 grams of para-phenylphenol. The resin produced was at least dispersible in xylene when hot, giving the appearance of solubility. When the solution cooled, obvious separation took place. For this reason 100 grams of diethyleneglycol diethylether were added to the finished resin mixture, when hot, so as to give a suitable solution when cold.

A small sample was taken before adding the diethyleneglycol diethylether and the xylene evaporated in order to determine the character of the resin. The solvent-free resin was opaque and reddish-black in color. It was soft and pliable in consistency.

Example 22a The same procedure was followed as in Example 14a, except that 176 grams of para-cyclohexylphenol were employed instead of the paratertiary butylphenol. The solvent-free resin was clear, dark red in appearance, soft to pliable in consistency, and xylene-soluble.

Example 23a The same procedure was followed as in Example 14a, except that the phenol employed was commercial styrlyphenol and the amount employed was 198 grams. The resin was soft-topliable, reddish-black in color, and xylene-soluble.

Example 24a Grams Para-tertiary amylphenol (1.0 mole) 164 Heptaldehyde (1.0 mole) 114 Concentrated H2504 2 Xylene 100 boiling aldehyde was added by means of the separatory funnel arrangement. Thus, the phenol, acid catalyst, and solvent were combined in a resin pot by the same procedure used as in Example 14a. The resin, after removal of the solvent by distillation, was clear, dark amber in color, had a soft, tacky appearance and was xylene-soluble.

Example 25a Grams Para-secondary butylphenol (1.0 mole) 150 Heptaldehyde (1.0 mole) 114 Concentrated H2804 2 Xylene 100 The same procedure was employed as in Example 24a. The solvent-free resin had physical characteristics similar to those of the resin of Example 24a.

Xylene Example 26a Grams Para-tertiary butylphenol (1.0 mole) Heptaldehyde (1.0 mole) 114 Concentrated H2804 2 Xylene 100 This resin was prepared as in Example 24a preceding, with the resulting solvent-free resin being a clear. dark amber color, semi-hard or pliable, and xylene-soluble.

Example 27a Grams Para-phenylphenol (1.0 mole) Heptaldehyde (1.0 mole) 114 Concentrated H2804 2 Xylene 100 The resin was prepared as in Example 24a. The solvent-free resin was slightly opaque, dark amber in color, soft in fluid, and sufliciently xylene-dispersible to permit subsequent oxyalkylation.

Example 28a Grams Para-cyclohexylphenol (3.0 molas) 528 Heptaldehyde (3.0 moles) -l 342 Concentrated H2804 6 Xylene 500 This resin, made as in Example 24a, in solventfree form was clear, dark amber to black in color, semi-soft to pliable and xylene-soluble.

Example 29a Grams Para-tertiary amylphenol (1.0 mole) 164 Benzaldehyde (1.0 mole) 106 Concentrated H2804 2 Xylene 100 This resin, made as in Example 24a, in solventfree form was clear, dark red, hard, brittle, had a melting point of ISO-165 C., and was xylenesoluble.

Example 30a Grams Para-secondary butylphenol (1.0 mole) 150 Benzaldehyde (1.0 mole) 106 Concentrated H2804 2 Xylene 10 0 This resin, made following the procedure employed in Example 24a, in solvent-free form was clear, mahogany in color, semi-hard or pliable and xylene-soluble.

was a clear, hard, brittle, reddish amber colored resin, which was xylene-soluble, and had a melting point of -185 C. -It was to some degree heat curable.

Example 32a Grams Para-phenylphenol (1.5 moles) 255 Benzaldehyde (1.5 moles) 159 Concentrated H2804 20g This resin was made as in Example 24a. The resulting solvent-free resin was clear, dark red. hard, and brittle, with a melting point of 200-205 C. It was somewhat heat curable, and almost completely soluble in xylene, with some insoluble ma rial which was dispersible. It was suitable for subsequent oxalkylation.

Example 33a Grams Para-cyclohexylphenol (3.0 moles) 528 Benzaldehyde (3.0 moles) 818 Concentrated H1804 6 Xylene 500 This resin, formed by combining the above reactants according to the procedure employed in Example 24a. was hard, brittle, xylene-soluble, reddish-black in color, and had a melting point The above reactants were combined according to the procedure followed in Example 24a. The resulting solvent-free resin was clear, dark amber in color, soft to pliable, and xylene-soluble.

Example 35a Grams Para-secondary butylphenol 150 Propionaldehyde 96% 60.5 Concentrated H2804 2 Xylene 100 This resin was prepared according to the procedure employed in Example 24a. The resulting solvent-free resin was clear, soft to fluid, dark amber in color, and was xylene-soluble.

Example 36a Grams Para-tertiary butylphenol (1.0 mole) 150 Propionaldehyde 96% (1.0 mole) 60.6 Concentrated H2S04 2 Xylene 100 This resin was prepared according to the procedure employed in Example 24a. The resulting solvent-free resin was clear, dark amber in color, xylene-soluble, hard and brittle, and has a melting point of 80-85 C.

Example 37a y Grams Para-phenylphenol (3.0 moles) 510 Propionaldehyde, 96% (3.0 moles) 182 Concentrated H2804 6 Xylene 500 The resulting resin, prepared according to directions in Example 24a, when solvent-tree was clear, dark amber in color, xylene-soluble, hard and brittle, and had a melting point oi. 84-90 C.

Eaample'39a V H Grams Para-tertiary amylphenol 164 2-ethyl-3-propyl acrolein 126 Concentrated H2804 2 Xylene 100 The procedure employed was the same as for the use of heptaldehyde, as in Example 24a. The resulting solvent-free resin was dark amber to black in color, and soft to fluid in consistency. It was xylene-soluble.

Example 40a Grams Para-tertiary butylphenol 150 2-ethyl-3-propyl acrolein 126 Concentrated H2504 2 Xylene 100 The procedure employed was the same as for the use 01' heptaldehyde, as in Example 24a. The

appearance oi the resin was the same as the resin of the Example 39a.

Example 41a Grams Commercial para-.octylphenol 206 2-ethyl-3-propyl acrolein 126 Concentrated H2804 2 Xylene 100 The procedure employed was the same as for the use of heptaldehyde, as in Example 24a. The appearance of the resin was the same as the resin of Example 39a.

Example 42a Grams Para-tertiary amylphenol -164 Furfural I 96 Potassium carbonate 8 The furiural was shaken with dry sodium carbonate prior to use, to eliminate any acids, etc. The procedure employed was substantially that described in detail in Techanical Bulletin No. 109 of the Quaker Oats Company, Chicago, Illinois. The above reactants were heated under the reflux condenser for two hours in the same resin pot arrangement described in Example 1a. The separatory funnel device was not employed. No xylene or other solvent was added. The amount of material vaporized and condensed was comparatively small except for the water of reaction. At the end of this heating or reflux period, the trap was set to remove the water. The maximum temperature during and after removal of water was approximately 202 C, The

material in the trap represented 16 cc. water and Example 43a I Grams Para-tertiary amylphenol 164 Furfural (carbonate treated) '10 Potassium carbonate 3.2

The procedure employed was the same as that of Example 42a. The amount of water distilled Monoalkyl (Cm-Cap, principally Cn-Cu) was '10 cc. and the amountof furfural, 8 cc. Theresin was 'a bright black, xylene-soluble resin, semi-pliable to hard.

benzene monosulfonic acid sodium salt Xylene 200 The above reactants were combined in a resin pot similar to that previously described, equipped with stirrer and reflux condenser. The reactants were heated with stirring under reflux for 2 hours at 100 to 110 C. The resinous mixture was then permitted to cool sufllciently to permit the addition of 15 ml. of glacial acetic acid in 150 00. E20. On standingfia separation was eflected, and the aqueous lower layer drawn oil. The upper resinous solution was then washed with '300 ml. of water to remove any excess HCHO, sodium acetate, or actlc acid. The xylene was then removed from the resinous solution by distilling under vacuum to 150 C. The resulting resin was clear light amber in color, and semi-fluid or tacky in consistency.

' Example 45a Grams Para-secondary butylphenol 450 Formaldehyde, 37% 528 NaOH in 30 cc. H2O 6.8

Monoalkyl (Cm-C20, principally C12-C14) benzene monosulfonic acid sodium salt 2 Xylene 200 The same procedure was followed as in Example 44a. The resulting solvent-free resin was clear, light amber in color, and semi-fluid or tacky in consistency.

Example 46a Grams Para-phenylphenol 510 Formaldehyde, 37% 528 NaOH in 30 cc. H20 6.8

Monoalkyl (Cm-C20, principally C12-C14) benzene mcnosulfonic'acid sodium salt 2.0 Xylene 500 solvent-free resin had a grayish-white crystalline structure, and was hard, brittle, non-xylene-soluble but soluble in a xylene-diethyleneglycol diethylether mixture. This crystalline structure in phenylphenol resins has been noted in the literature.

Example 47a Grams Para-cyclohexylphenol 528 Formaldehyde, 37% 528 NaOH in 30 cc. H1O 6.8

Monoalkyl (Clo-C20, principally 012-014) benzene monosulfonic acid sodium salt 2.0 Xylene 300 This resin was made and worked up in the same manner as in Example 46a. The resin, after distillation and standing overnight, developed the same type of crystalline structure noted in the resin of the Example 46a. However, on

cooling immediately after distillation,the resulting product was clear, light amber in color, and fairly soft in consistency.

Example 480 Grams Para-tertiary butylphenol 450 Formaldehyde, 30% 652 NaOH in 30 cc. H2O.. 6.8

Monoalkyl (Clo-C20, principally Cir-C14) benzene monosulfonic acid sodium salt... Xylene The same procedure was followed as in Example 44a. The resulting resin was deep red in color, clear, and soft or semi-fluid in consistency.

Example 49a This resin was prepared as in Example 44a except that the paratertiary amylphenol-formaldchyde ratio was 1 to 1.1 moles. The resulting solvent-free resin was dark red in color, clear, .and semi-hard or pliable in consistency.

Example 50a The resin was prepared as in Example 48a except that the paratertiary butylphenol-iormaldehyde ratio was 1 to 1.1 m'oles. The resulting solvent-free resin was dark red in color, clear, hard, brittle, and had a melting point of -105 C.

This resin was prepared as in Example 44a. A small amount, approximately 1%, of an insoluble, infusible flocculent precipitate was noted dispersed throughout the resinous solution. This was filtered out before distillation. The resin, after vacuum distillation to C. to remove the solvent, was dark red in color, clear, hard and brittle, with a melting point of 113-117 0.

Example 52a Resin of Example 44a. was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting product was a hard, brittle resin, xylenesoluble, and having a melting point of 145-150 C.

Example 53a Resin of Example 45a was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting roduct was hard, brittle, black in color, xylene-insoluble, and infusible up to 220 0. However, if the vacuum distillation was taken to only or C., at 25 mm. Hg the resulting product was xylene-soluble and had a melting point of approximately 170 C.

Example 54a Resin of Example 46a was subjected to vacuum distillation to 225 CL, at 25 mm. Hg. The resulting roduct was opaque or crystalline, xylenedispersible, and soluble in a mixed solvent of 75% xylene and 25% diethyleneglycol diethylether, with a melting point of 100-105" C.

Example 55a Resin of Example 47a was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting'product was opaque or'crysta'lline, dark brown in color,-xylene-soluble, and semi-hard or pliable in consistency;

Example 56a Example 57a Resin of Example 49a was subjected to vacuum distillation to 225 C. at 25 mm. Hg. The resulting product was dark amber to black in color, xylene-soluble, hard and brittle, with a melting point of 145-150 C.

Example 58a Resin of Example 50a was subjected to vacuum distillation to.225 Cu, at 25 mm. Hg. The resulting resin was black in color, hard and brittle, xylene-dispe'rsible, and soluble in. a mixed solvent of 75% xylene and 25% diethyleneglycol diethyiether, with a melting point of 165-170 C. It was also heat curable. I

Example 59a Resin of Example 51a was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting resin was dark amber in color, xylene-soluble,

hard and brittle, with a melting point of 115- Example 60a Grams Commercial para-tertiary amylphenol (described in Example 5a) 328 Formaldehyde, 37% 352 NaOH in 20 cc. H20 4.5

Monoalkyl (Cm-C20, principally elk-C) benzene monosulfonic acid sodium salt 1.5

The above reactants were refluxed with stirring for 2 hours. 200 grams or xylene were then added and the whole cooled to 90100 C., and the NaOH neutralized with 10 cc. glacial acetic acid in 100 cc. H2O. The mass was allowed to stand, etfecting a separation. The lower aqueous layer was withdrawn and the upper resinous solution was washed with water. After drawing oil! the wash water, the xylene solution was subjected to vacuum distillation, heating to 150 C. The resulting solvent-free resin was xylene-soluble. soft or tacky in consistency, and pale yellow or light amber in color.

0n heating further, without vacuum distillation, the following physical changes were noted:

Heated to 160 C.Soft, tacky, pale yellow Heated to 190 C.Hard, fairly brittle, pale yellow-low melting point I Heated to 200 C.-Hard, fairly brittle, pale yellow-105115 C. melting point Heated to 225 ,C.-.-Hard, brittle, amber-120- 125 C. melting point 1 Heatedto 250 C.--Hard, brittle, dark amber- 128-135 C. melting point Heated to 275 C.-Very brittle, deep brown- 155-160 C. melting point The above distillation was without the use of vacuum. It illustrates that heating alone, or heating with vacuum, changes a low-stage resin into a medium or high-stage resin.

Example 62a This resin was obtained by the vacuum distillation of resinof Example 8a. Vacuum distillation was conducted up to 225 C. at 25 mm. Hg. The resulting resin was xylene-soluble, hard, brittle, reddish black in color, with a melting point of 140-145? C. Note that this resin, prior to vacuum distillation, was soft to pliablein consistency.

Example 63a I This resin was obtained by the vacuum distillation of resin of Example 10a. Vacuum distillation was conducted up to 225. C. at 25 mm. Hg.

The resulting resin was xylene-dispersible, soluble in a mixture of xylene and diethyleneglycol. diethylether dark brown in color, and hard and brittle in nature. It had a melting 'point of 180-185 C. This was moderately higher than the resin prior to vacuum distillation.

Example 64a This resin was obtained by the vacuum distillation of resin of Example 9g. Vacuum distillation was conducted up to 225C. at 25 mm. Hg. The resulting resin was semi-hard but still contained some diethyleneglycol diethylether. Unquestionably, if completely separated irom'this solvent it would have been a hard solid resin. Such residual solvent was not eliminated le there be danger of pyrolysis.

Example 65a This resin was'obtained by the vacuum distillation of resin of Example 16a. Vacuum-distillation was conducted up to 225C. at 25 mm. Hg. The resulting resin had the same physical characteristics as the undistilled resin except that it was slightly more viscous.

Example 66a This resin was obtained by the vacuum dis tillation of resin of Example 15a. Vacuum distillation was conducted up to 225 C. at 25 mm. Hg. The resulting resin was semi-hard to pliable.

Example 67a This resin was obtained by the vacuum distillation of resin of Example 20a. Vacuum distillation was conducted up to 225 C. at 25 mm. Hg. The resulting resin was hard to pliable.

In the immediately preceding example describing the production of resins by the vacuum distillation of resins of earlier examples, the vacuum used was approximately 25 mm. and the temperature was brought up to 225 C. Generally speaking, this is about the maximum temperature which is usable. and if the products obtained on distilling to this temperature, even if xylene-soluble, give insoluble or rubbery prod- 'ucts on oxyethylation, the temperature used should be lower. We have found that using a temperature of C. at 25 mm. gives very satis- Vacuum distillaaaoaaro factory compounds which have little tendency to form rubbery derivatives during oxyethylation.

Example 68a Grams Commercial para-tertiary amylphenol (described in Example a) 184 Formaldehyde, 37% 81 Monoalkyl (Cm-C20, principally Cn-Cu) benzene monosulfonic acid sodium salt .8 Xylene 200 No catalyst was added in this example. The reactants were placed in an autoclave and stirred while heating to a temperature of approximately 160 C. The total period of reaction was 5 hrs. During the early part of this period the temperature was 156 C. with a gauge pressure of 110 pounds. During the last part of the period, probably due to'the absorption of formaldehyde, the pressure dropped to '75 pounds gauge pressure while the temperature held at about 150 C. After this 5 hour reaction period the autoclave was allowed to cool. The liquids were withdrawn and the xylene solution of the resin was decanted away from the small aqueous layer. The xylene solution, containing a bit of the aqueous layer carried over mechanically, was subjected to vacuum' distillation up to 150 C. at 25 mm. Hg.

The resulting resin was fairly hard and brittle, xylene-soluble, dark, amber in color, with a melting point of 55 to 66 C., and a molecular weight of 490. If desired, one may use consid- Example 69a Grams Menthyl phenol, technically pure (0.1 mole) 232 Formaldehyde 37% (1.0 mole) 81 Concentrated HCl 2 Monoalkyl (Clo-C20, principally C12-C14) benzene monosulfonic acid sodium salt--- 2 Xylene 200 The phenol, formaldehyde, acid catalystand solvent were combined in the resin pot above described. Heat was applied with gentle stir-' ring and the temperature was raised to 80-85" C., at which point a mild exothermic reaction took place. This reaction raised the temperature to approximately 105-110 C. The reaction mixture. was then permitted to reflux at 100-105 C. for between one and one and onehalf hours. The reflux trap arrangement was then changed from the reflux position to the normal water entrapment position. The water of solution and the water of reaction were permitted to distill out and collect in the trap. As the water distilled out, the temperature gradually increased to approximately 150 C. which required between 1.5 to 2 hours. At this point the water recovered in the trap, after making allowance for a small amount of water held up in the solvent, corresponded to the expected quantity.

The solvent solution so obtained was used as such in subsequent oxyalkylation steps. We have also removed the solvent by conventional means, such as evaporation, distillation or vacuum distillation, and we customarily take a small sample of the solvent solution and evaporate the hard, brittle and had a melting point of about 115-120 (2.

Example 70a Grams Nonylphenol (para) 3.0 moles 660 Formaldehyde 37% (3.0 moles) 243 Concentrated HCl 9 Monoalkyl (Cw-C20, principally 012-014) benzene monosulfonic acid sodium salt 2.5 Xylene 300 The procedure followed was the same as that used in Example 69a. The phenol employed was a heavy, sirupy liquid, largely or almost entirely para with possibly a small percentage of ortho present. The solvent-free resin was clear, reddish amber in color and semi-soft or pliable in consistency.

Example 71a Grams Crude para-cumylphenol (1.27 moles) 268 Formaldehyde 37% (2.0 moles) 162 Concentrated HCl 2.5 Monoalkyl (Cm-C20, principally Cir-C14) benzene monosulfonic acid sodium salt 1 Xylene 250 Example 72a Grams 49 Para-decylphenol (1.0 mole) 234 "Formaldehyde 37% (1.0 mole) 81 H0] (concentrated) 2 Monoalkyl (Cfo-Czo, principally C12-C14) benzene monosulfonic acid sodium salt 1.2 Xylene 200 v solvent to note the characteristics of the solvent- The procedure followed was the same as that used in Example 69a preceding. The phenol was a straw colored liquid having a little phenolic odor. The solvent-free resin obtained was reddish amber in color and semi-soft or pliable in consistency. I

Example 73a Grams Para-dodecylpheno1'(l.0 mole) 262 Formaldehyde 37% (1.0 mole) 81 HCl (concentrated) 3.5

Monoalkyl (Cm-C20, principally C12C14) benzene monosulfonic acid sodium salt 2.5 Xylene 250 The procedure followed was the same as that used in Example 69a. The phenol was a straw colored liquid having a little phenolic odor. The solvent-free resin obtained was deep red in color and semi-soft or pliable in consistency.

Example 74a Grams Nonylphenol (1.0 mole) 220 Formaldehyde 3'7 (0.865 mole) 70 Glyoxal 30% (0.065 mole) 12.5

Concentrated HCl 2 Monoalkyl (Clo-C20, principally C12Cl4) benzene monosulfonic acid sodium salt 0.8 Xylene The procedure followed was the same as tha used in Example 69a preceding. When glyoxal is used it is not unusual for a very small amount of carbonaceous material to be formed. This was true in this case as the amount formed represented a few per cent of the total amount of resin. This was removed by merely filtering the xylene solution. The solvent-free resin was clear in appearance, reddish amber in color and semi-hard to pliable in consistency.

Example 7 5a Grams Menthylphenol, technically pure (1.0 mole)-.. 232

Acetaldehyde (1.0 mole) 44 Concentrated H1804 2 Xylene 100 The phenol, acid catalyst, and 50 grams of the xylene were combined in the resin pot previously described under Example 1a. The initial mixture did not include the aldehyde. The mixture was heated with stirring to approximately 150 C. and permitted to reflux.

The remainder of the xylene, 50 grams, was '1 then mixed with the acetaldehyde; and this mixture was added slowly to the materials in the resin'pot, with constant stirring, by means of the separatory funnel arrangement previously mentioned in the description of the resin pot in Example 1a. Approximately 30' minutes were required to add this amount of diluted aldehyde. A mild exothermic reaction was noted at the first addition of the aldehyde. The temperature slowly dropped, aswater of reaction formed, to

about 100 to 110 C., with the reflux temperature being determined by the boiling point of water. After all the aldehyde had been added, the reactants were permitted to reflux for between an hour to an hour and a half before removing the water by means of the trap arrangement. After the water was removed the remainder of the procedure was essentially the same as in Example 69a. The solvent-free resin was hard but not brittle, reddish amber in color and had a melting point of about 50 to 55 C.

Example 76a Grams Nonylphenol, para (0.773 moles) 170 Acetaldehyde (.773 mole) 34 Concentrated H2804 3 Xylene 75 The same procedure was followed as in Example 75a, except that nonylphenol was used instead of menthylphenol. The solvent free resin was reddish amber in color and soft to pliable in consistency.

Example 77a Grams Menthylphenol (3.0 moles) 696 Heptaldehyde (3.0 moles) 343 Concentrated H380 6 Xylene- 500 32 dark red in color, had a soft, tacky appearance and was xylene-soluble.

Example 78a 7 4 Grams Nonvlphenol (1.0 mole) 22o Heptaldehyde (1.0 mole) 114 Concentrated H2804 2 -Xylene 150 The same procedure was followed as in Example 77a preceding. The solvent-free resin was dark amber in color and semi-fluid or tacky in consistency.

Example 79a V V Z V V Grams Menthylphenol (1.0 mole) 232 Benzaldehyde (1.0 mole) 106 Concentrated H2804 2 Xylene 150 The procedure followed was the same as in Example 77a. The solvent-free resin was semihard to pliable and reddish amber in color.

Example 80a Grams Nonylphenol (1.5 moles) 330 Benzaldehyde (1.5 moles) 159 Concentrated H2804 3 Xylene 200 The procedure followed was the same as in Example 77a. The solvent-free resin was clear, semi-soft to pliable and dark amber in color.

Example 81a Grams Menthylphenol (1.0 mole) M. 232 Propionaldehyde 96% (1.0 mole) 60.5 Concentrated H2804 2 40 Xylene 150 The same procedure was followed as in Example 77a. The solvent-free resin was dark amber in color, semi-hard or pliable in consistency, with a tendency towards tackiness. I

Example 82a Grams Non'ylphenol 220 Propionaldehyde 96% (1.0 mole) 60.5 Concentrated H2804 2 Xylene 150 The same procedure was followed as in Example 77a. The solvent-free resin was dark amber in color and semi-fluid or tacky in consistency.

Example 83a Grams Nonylphenol (1.0 mole) 220 2-ethyl-3-propyl acrolein (1.0 mole) 126 Concentrated H1804 2.5

Xylene 100 The same procedure was followed as in Example 77a. The solvent-free resin was black in color and soft to fluid in consistency.

Example 84a Grams Menthylphenol (1.0 mole) 232 2-ethyl-3-propyl acrolein (1.0 mole) 126 Concentrated H2804 2.5

Xylene 150 The same procedure was followed as in Example 77a. The solvent-free resin was black in color and soft to fluid in consistency.

I Nonylphenol (3.0 moles) grams Monoalkyl (Cm-C20, principally Cir-C14) benzene monosulfonic acid sodium salt 2 Xylene 300 The above reactants were combined in a resin pot similar to that previously described, equipped with stirrer and reflux condenser. The reactants were heated with stirring under reflux for 2 hours at 100 to 110 C. The resinous mixture was then permitted to cool sufllciently to permit the addition of 15 ml. of glacial acetic acid in 150 cal-I20. On standing, a separation was eifected and the aqueous lower layer drawn ofl. The upper resinous solutionwas then washed with 300 ml. of water to remove any excess HCHO, sodium acetate, or acetic acid. The xylene was then removed from the resinous solution by distilling under vacuum to 150 C. The solvent-free resin was light amber in color, nonbrittle, and semi-pliable to hard.

Example 86a 660 Formaldehyde 30% (6.6 moles) do 652 NaOH in 30 cc. H2O do 6.8 Monoalkyl (Cw-C20, principally 012-014) benzene monosulfonic acid sodium salt "grams" 2 Xylene do 300 Glacial acetic acid ml 15 The procedure used was the same as that of Example 85a. The solvent-free resin was clear, dark amber in color and soft to fluid in consistency.

Example 87a Nonylphenol (3.0 moles) grams 660 Formaldehyde 30% (3.3 moles) do 330 NaOH in 30 cc. H20 do 6.8 Monoalkyl (Cm-C20, principally Ciz-Cn) benzene monosulfonic acid sodium salt grams 2 Xylene do 100 Glacial acetic acid mi 15 The same procedure was followed as in Example 85a. The solvent-free resin was clear, dark red in color and semi-fluid or tacky in consistency.

Example 88a Grams Nonylphenol (1.0 mole) 220 Furfural (NazCOa treated) (1.0 mole) 96 Potassium carbonate 12 Xylene 200 The furfural was shaken with dry sodium carbonate prior to use to eliminate any acids, etc. The procedure employed was substantially that described in detail in Technical Bulletin No. 109 of the Quaker Oats Company, Chicago, Illinois. The materials, except the xylene, were heated under the reflux condenser for two hours in the same resin pot arrangement described in Example 1a. At the end of this heating or reflux period the trap was set to remove the water, and the xylene added after most of the water had distilled. The maximum temperature during and after removal of water was approximately 205 C. The resin was a reddish black, clear resin, xylene-soluble, and semi-soft to pliable in consistency. When the resinification was complete, as a matter of convenience instead of pouring the hot resin and subsequently dissolving it in xylene, the amount of xylene indicated was added simply for purposes of dilution.

Example 89a ,Grams Menthylphenol (1.0 mole) 232 Furfural (NaaCO: treated) (1.0 mole) 96 Potassium carbonate 12 Xylene 200 The procedure followed was identical with that The solvent-free resin was reddish black in color, hard, brittle, with a melting point of 158 to 163 C., and showed a definite tendency towards being heat curable. 7

Example 90a A duplication of the resin described under the heading of Example 86a was prepared and sub- Jected to distillation. Distillation without vacuum was flrst employed to eliminate the xylene. After the elimination of xylene the resin was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting resin was black in color, semi-fluid but of distinctly greater viscosity or hardness than the undlstilled resin, and was still perfectly xylene-soluble.

Example 91a Example 92a A duplicate of the resin described in Example 69a was prepared and subjected to vacuum distillation in the same manner as described in Example 90a. The resulting resin was a hard, brittle, amber colored resin, xylene-soluble and ha a melting point of 145 to 150 C.

Eaample 93a A duplicate of the resin described in Example 70a was prepared and subjected to distillation, including vacuum distillation, in the same manner as described in Example 90a. The resulting resin was a clear, hard, brittle, xylene-soluble resin, amber colored, and had a melting point of to C.

Example 94a A duplicate of the resin described in Example.

85a was prepared and subjected to distillation, including vacuum distillation, in the same manner as described in Example a. The resulting prodnot was hard and brittle, with a melting point of to C. -Otherwlse the physical characteristics were approximately the same as in the non-distilled product.

Example 95a Grams Nonylphenol (31 moles) 6,820 Formaldehyde 37% (42 moles) 3,430 NaOH (in 200 cc. H2O) 93 Xylene 2,040

The above reactants were combined in a 5- 35 gallon autoclave and heated with stirring in the following manner:

Pounds Tem- Time per Square perature ch The reaction was stopped at this point, sumcient cooling water was applied to lower the temperature to approximately 80 C., or cool enough to permit opening the autoclave and adding 202 grams of glacial acetic acid to neutralize the NaOH.

The product was-then removed from the autoclave and the resin solution diluted further so as to effect a ready separation of the aqueous layer. After twice washing with water to remove the excess formaldehyde, acetic acid and formed salt, the resin was subjected to vacuum distillation to 149 C. at mm. Hg vacuum. The resulting resin was reddish black in color, xylene-.

36 the water and unreacted formaldehyde. After twice washing the xylene resin solution with water to assure the removal of any unreacted formaldehyde, the solution was subjected to vacuum distillation (25 mm.) to 145 C., to remove the xylene.

soluble, hard but not brittle, and had a melting point of 85 to 90 C.

Example 96a Grams Nonylphenol (22.5 moles) 4,980 Formaldehyde (37 25.5 moles) 2,076

Monoalkyl (Clo-C20, principally Gin-C14) benzene monosulfonic acid sodium salt 15 NaOH (in 200 cc. mo) 67 Xylene 4,000

' C., was semi-hard to pliable, amber colored, and

exylene-soluble. If -the vacuum distillation is further carried to 200 C., the resulting product is a hard, brittle resin with a melting point of 90 to 95 C. It is amber in color and xylene-soluble.

Example 97a Grams Nonylphenol (34 moles) 7,470 Formaldehyde 37% (38 moles) 3,114 Xylene 2,020 Catalyst None The above reactants were combined in a 5- gallon autoclave. 'They were heated with stirring under pressure for a total heating time (time starting when temperature reached 100 C.) of 5 hours with a maximum temperature of 200 C., and maximum gauge pressure of' 235 pounds per square inch.

After removing the resin mixture from the autoclave, it was diluted further with approximately 7000 grams of xylene. This was done to thin the resin sufllciently to permit a ready-separation of The resulting resin was clear, xylene soluble, amber colored and semi-hard or pliable in consistency.

Example 98a Grams Decylphenol 158 Formaldehyde (37%) 54.6 Concentrated HCl 2 Monoalkyl (Cm-C20, principally 012-014) benzene monosulfonicacld sodium salt. 1

Xylene 150 The procedure followed was that of Example 1a. The solvent-free resin was clear, reddish amber in color, xylene-soluble and hard and brittle in consistency. It had a melting point of 110 to 115 C.

Example 99a Grams Dodecylphenol 262 Formaldehyde (37%) 90 Concentrated HCl 3 Monoalkyl (Clo-C20, principally C12-C14) benzene monosulfonic acid sodium salt 1 Xylene 100- The procedure followed was that of Example 1a. The solvent-free resin was clear, reddish-amber in color, xylene-soluble, and soft to semi-fluid in consistency.

Example 100a Dodecylphenol (1.0 mole) grams 262 Formaldehyde 37% (1.1 moles) do 90 NaOH in 30 cc. H2O do 4.5 Monoalkyl (Cw-C20, princiupally 012-014) benzene monosulfonic acid sodium salt grams 1.0 Xylene do 200 Glacial acetic acid ml 10 The procedure followed was that of Example 85a. The solvent-free resin was clear, reddishamber in color, xylene-soluble, and soft to semifluid in consistency.

Example 101a Grams Dodecylphenol 262 Benzaldehyde 106, Concentrated H2804 2.5 Xylene 100 The procedure followed was that of Example a. The solvent-free resin was clear, reddishblack in color, xylene-soluble, and soft to pliable in consistency.

Example 102a Grams Decylphenol 234 Formaldehyde 37% 81 NaOH in 20 cc. H2O 4.5

Monoalkyl (Cm-C20, principally C12-C14) benzene monosulfonic acid sodium salt Xylene The procedure used was the same as that of Example 85a. The solvent-free resin was opaque, xylene-dispersible, amber in color and semi-hard 75 or pliable in consistency.

Example 103a Grams Menthyl phenol (1.0 mole) 232 Nonylphenol (1.0 mole) 220 Formaldehyde 37% (2.0 moles) 162 Concentrated HCl 4 Monoalkyl (Clo-C20, principally Cir-C14) benzene monosulfonic acid sodium salt 1.5 Xylene 200 the structure of the substituent radical. In such cases, the phenols meant are either the commercial products distributed under these names, or, if the products are not commercially available, the products obtained by customary syntheses from phenol, meta-cresol or 3,5-xylenol, and consist mainly of the para-substituted product, usually associated with some of the ortho-substituted product, perhaps a very small proportion of metasubstituted material, some impurities, etc. Also it is to be understood that all of the products of the foregoing examples, unless it is otherwise stated in the example, are soluble in xylene, at least to an extent sufficient to permit the use of xylene as the solvent in oxyalkylation.

As far as themanufacture of resins is concerned it is usually most convenient to employ a catalyst such as illustrated by previous examples.

Previous reference has been made to the use of a single phenol as herein specified or a single reactive aldehyde or a single oxyalkylating agent. Obviously, mixtures of reactants may be employed, as for example a mixture of para-butylphenol and para-amylphenol, or a mixture of para-*butylphenol and para-hexylphenol, or parabutylphenol and para-phenylphenol. It is extremely difficult to depict the structure of a resin derived from a single phenol. When mixtures of phenols areused, even in equimolar proportions, the structure of the resin is even more indeterminable. In other words, a mixture involving para-butylphenol and para-amylphenol might have an alternation of the two nuclei or one might have a series of butylated nuclei and then a series of amylated nuclei. If a mixture of aldehydes is employed, for instance, acetaldehyde and butyraldehyde, or acetaldehyde and formaldehyde, or benzaldehyde and acetaldehyde, the final structure of the resin becomes even more complicated and possibly depends on the relative reactivity of the aldehydes. For that matter, one might be producing simultaneously two diflerent resins, in what would actually be a mechanical mixture, although such mixture might exhibit some unique properties as compared with a mixture of the same two resins prepared separately. Similarly, as has been suggested, one might use a combination of oxyalkylating agents; for instance, one might partially oxyalkylate with ethylene oxide and then finish oiI with propylene oxide. It is understood that the use of oxyalkylated derivatives of such resins, derived from such plurality of reactants instead of being limited to a single reactant from each of the three classes, is contemplated and here included for the reason that they are obvious variants.

Having obtained a suitable resin of the kind described, such resin is subjected to treatment with a low molal reactive alpha-beta olefin oxide so as to render the product distinctly hydrophile in nature as indicated by the fact that it becomes seli-emulsifiable or miscible or soluble in water, or self-dispersible, or has emulsifying properties. The olefin oxides employed are characterized by the fact that they contain not over 4 carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide. Glycide may be, of course, considered as a hydroxy propylene oxide and methyl glycide as a hydroxyl butylene oxide. In any event, however, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of or substituted ethylene oxides. The solubilizing eflect of the oxide is directly proportional to the percentage of oxygen present, or specifically, to the oxygencarbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surfaceactive properties. However, the ratio, in propylene oxide, is 1:3, and in butylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the resin composition is such as to make incorporation of the desired property practical. In other cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are .usable in conjunction with the three more favorable alkylene oxides in all cases. For instance, after one or several propylene oxide or butylene oxide molecules have been attached to the resin molecule, oxyalkylation may be satisfactorily continued using the more favorable members of the class, to produce the desired hydrophile product.

Used alone, these two reagents may in some cases fail to produce sufliciently hydrophile derivatives because of their relatively low oxygen-carbon ratios.

Thus, ethylene oxide is much more effective than propylene oxide, and propylene oxide is more effective than butylene oxide. Hydroxy propylene oxide (glycide) is more effective than propylene oxide. Similarly, hydroxy butylene oxide (methyl glycide) is more eifective than butylene oxide. Since ethylene oxide is the cheapest alkylene oxide available and is reactive, its use is definitely advantageous, and especially in light of its high oxygen content. Propylene oxide is less reactive than ethylene oxide, and butylene oxide is definitely less reactive than propylene oxide. On the other hand, glycide may react with almost explosive violence and must be handled with extreme care.

The oxyalkylation of resins of the kind from which the products used in the practice of the present invention are prepared in advantageously catalyzed by the presence of an alkali. Useful alkaline catalysts include soaps, sodium acetate, sodium hydroxide, sodium methylate, caustic potash, etc. The amount of alkaline catalyst usually is between 0.2% to 2 The temperature employed may vary from room temperature to as high as 200 C. The reaction may be conducted with or without pressure, i.e., from zero pressure to approximately 200 or even 300 pounds gauge pressure (pounds per square inch). In a general way, the method employed is substantially the same procedure as used for oxyallwlation of other organic materials having reactive phenolic groups.

It may be necessary to allow for the acidity of a resin in determining the amount of alkaline catalyst to be added in oxyalkylation. For instance, if a nonvolatile strong acid such as sulfuric acid is used to catalyze the resiniflcation reaction, presumably after being converted into a sulfonic acid, it may be necessary and is usually advantageous to add an amount of alkali equal stoichiometrically to such acidity, and include added alkali over and above this amount as the alkaline catalyst.

It is advantageous to conduct the oxyethylation in presence of an inert solvent such as xylene, cymene, decalin, ethylene glycol diethylether, diethyleneglycol, diethylether, or the like, although with many resins, the oxyalkylation proceeds satisfactorily without a solvent. xylene is cheap and may be permitted to be present in the final product used as a demulsiner, it is ,our preference to use xylene. This is particularly true in the manufacture of products from low-stage resins, i.e., of 3 and up to and including 7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the combined pressure due to xylene and also due to ethylene oxide or whatever other oxyalkylating agent is used. Under such circumstances it'may be necessary at times to use substantial pressures to obtain effective results, for instance, pressures up to 300 pounds along with correspondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such as xylene can be eliminated in either one of two ways: After the introduction of approximately 2 or 3 moles of ethylene oxide, for example, per phenolic nucleus, there is a definite drop in the hardness and melting point of the resin. At this stage, if xylene or a similar solvent has been added, it can be eliminated by distillation (vacuum distillation it desired) and the subsequent intermediate, being comparatively soft and'solvent-iree, can be reacted further in the usual manner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to completion with such solvent present and then eliminate the solvent by distillation in the customary manner.

Since Another suitable procedure is to use propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the powdered resin in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the original resin dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain some unreacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in any suitable manner.

Attention is directed to the fact that the resins herein described must be fusible or soluble in an organic solvent. soluble in one or more organic solvents such as those mentioned elsewhere herein. It is to be emphasized, however, that the organic solvent Fusibleresins invariably are I employed to indicate or assure that the resin meets this requirement need not be the one used in oxyalkylation. Indeed solvents which are susceptible to oxyalkylation are included in this group of organic solvents. Examples of such solvents are alcohols and alcohol-ethers. However,-where a resin is soluble in an organic solvent, there are usually available other organic solvents which are not susceptible to oxyalkylation, useful for the oxyalkylation step. In any event, the organic solvent solubleresin can be finely powdered, for instance to 100 to 200 mesh, and a slurry or suspension prepared in xylene or the like, and subjected to oxyalkylatiom' The fact that the resin is soluble in an organic solvent or the fact that it is fusible means that it consists of separate molecules. Phenol-aldehyde resins of the type herein specified posess reactive hydroxyl groups and are oxyalkylation susceptible.

Considerable of what is said immediately hereinafter is concerned with the ability to vary the hydrophile properties of the compounds used in the process from minimum hydrophile properties to maximum hydrophile properties. Even more remarkable, and equally diflicult to explain, are the versatility and utility or these compounds as one goes from minimum hydrophile property to ultimate maximum hydrophile property. For instance, minimum hydrophile property may be described roughly as the point where two ethyleneoxy radicals or moderately in excess thereof are introduced per phenolic hydroxyl. Such minimum hydrophile property or sub-surfaceactivity or minimum surface-activity means that the product shows at least emulsifying properties or self-dispersion in cold or even in-warm distilled water (15 to 40C.) in concentrations of 0.5% to 5.0%. These materials are generally more soluble in cold water than warm water, and may even be very insoluble in boiling water. Moderately high temperatures aid in reducing the viscosity oi. the solute under examination. Sometimes it one continues to shake a hot solution, even though cloudy or containing an insoluble phase, one finds that solution takes place to give a homogeneous phase as the mixture cools. Such self-dispersion tests are conducted in the absence of an insoluble solvent.

when the hydrophile-hydrophobe balance is above the indicated minimum (2 moles oi ethylene oxide per phenolic nucleus or the equivalent) but insufllcient to give a sol as described immediately preceding, then, and in that event hydrophile properties are indicated by the fact that one can produce an emulsion by having, present 10% to 50% of an inert solvent such as xylene. All that one need to do is to have a xylene solution within the range of 50 to parts by weight of oxyalkylated derivatives and 50 to 10 parts by weight of xylene and mix such solution with one,

.two or three times its volume of distilled water and shake vigorously so as to obtain an emulsion which may be of the oil-in-water type or the water-in-oil type (usually the former) but, in any event, is due to the hydrophile-hydrophobe balance of the oxyalkylated derivative. We prefer simply to use the xylene diluted derivatives, which are described elsewhere, for this test rather than evaporate the solvent and employ any more elaborate tests, it the solubility is not suflicient to permit the simple sol test in water previously noted.

If the product is not readily water soluble it may be dissolved in ethyl or methyl alcohol, 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING A HYDROPHILE OXYALKYLATED 2,4,6 C4- TO C12- HYDROCARBON SUBSTITUTED MONOCYCLIC PHENOLC1- TO C8- ALDEHYDE RESIN IN WHICH THE RATIO OF OXYALKYLENE GROUPS TO PHENOLIC NUCLEI IS AT LEAST 2:1 AND THE ALKYLENE RADICALS OF THE OXYALKYLENE GROUPS ARE SELECTED FROM THE CLASS CONSISTING OF ETHYLENE, PROPYLENE, BUTYLENE, HYDROXYPROPYLENE AND HYDROXYBUTYLENE RADICALS. 